JP2014088465A - Polyurethane resin composition for ink and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an ink having excellent printability, particularly, having excellent plate fog, and having excellent dispersion stability of pigment even without adding a pigment dispersant, and a printing ink using the composition.SOLUTION: Provided is a resin composition for an ink comprising a polyurethane resin (a) obtained by reacting a compound (I) covalently bonded to carbon in the resin and having an amino group and/or an imino group. Also provided is a printing ink comprising the composition. Also provided is a printed matter using the printing ink. Also provided is a laminate using the printing ink.

Description

  The present invention relates to a printing ink suitable for solvent recovery and reuse in which a solvent is composed of an organic solvent and / or water and recovery of a volatile solvent is facilitated during printing. Furthermore, the present invention relates to a printing ink suitable for solvent recovery and reuse in which 95% or more of the solvent is composed of a single organic solvent and water, and the recovery of the volatile solvent is facilitated during printing.

  In recent years, air pollution problems such as destruction of the natural environment, destruction of the ozone layer in the stratosphere, damage to agricultural products and destruction of forest resources due to acid rain in the lower stratosphere, and adverse effects on human bodies due to photochemical oxidants have become serious every day. It has become. For this reason, laws related to air environment conservation such as the enforcement of the PRTR Law to prevent this, the strengthening of regulations on the Odor Prevention Law, the reduction of carbon dioxide emissions under the Kyoto Protocol, the Air Pollution Control Law, the Saitama Prefecture Living Environment Conservation Ordinance, etc. It is getting stricter. In particular, in the gravure printing industry that uses and releases a large amount of organic solvents, interest in solvent recovery and reuse is increasing as a means to solve these problems.

  In fact, in the field of laminating adhesives and publishing gravure printing, the solvent species is designed to have a composition of toluene alone, and the volatile solvent is recovered and reused. This is because the recovery solvent can also be obtained with a single composition if it is a single solvent composition and can be easily reused as a diluting solvent for adhesives and inks.

  There are two types of gravure inks mainly used in the manufacture of soft packaging materials: organic solvent type and aqueous type. Among them, 90% or more of gravure inks used for plastic films and the like are organic solvent type inks. This is because the drying property, printing stability, and physical properties are high, and there are excellent characteristics as compared with the aqueous type. On the other hand, reduction of organic solvents is required in recent efforts for environmental protection. However, when switching to the water-based type, the low drying property and high surface tension peculiar to water, which is the dispersion medium, and the decrease in productivity due to the fact that the water-dispersed resin is difficult to re-disperse in water. , The deterioration of quality is inevitable, and the transition in the industry is not progressing.

  Under such circumstances, an approach to burn or recover the organic solvent volatilized in the drying process after printing has been studied. However, the combustion treatment generates a large amount of CO2, which is not preferable from the viewpoint of preventing global warming. Therefore, recovery processing is expected to become mainstream. However, since the current gravure ink uses a wide variety of organic solvents, it is not easy to reuse and reuse the recovered solvent.

  In view of this, there has been disclosed an ink that has been devised to promote recovery and reuse by using an alcohol-soluble urethane urea resin having a hydroxyl group (see, for example, Patent Document 1). However, this technique has insufficient pigment dispersibility. Furthermore, using an alcohol solvent as a reaction solvent, the linear urethane prepolymer (A) having an isocyanate group bonded to carbon of an aliphatic hydrocarbon at both ends and further having a carboxyl group in the molecular side chain; , A reaction with diamine (B) to produce an alcohol-soluble urethane resin by neutralizing the carboxyl group in the linear urethane prepolymer (A) with a base, and printing ink is proposed using the resin as a binder resin (For example, refer to Patent Document 2). Also, a composition for printing ink using a single alcohol solvent using a single type of alcohol solvent and 95% or more of the solvent component and a specific polyurethane polyurea resin that completely dissolves in water has been proposed. (For example, refer to Patent Document 3). However, although both techniques are excellent in dryness, adhesion, etc., a dispersant is essential at the time of pigment dispersion, or plate fog is at a level that does not reach the practical range.

JP 2004-175867 A JP2002-293860 International Publication WO2012 / 008339

  Accordingly, an object of the present invention is to use an ink resin composition that is excellent in printability, in particular, excellent in plate fog, and excellent in pigment dispersion stability without the addition of a pigment dispersant, and the composition. It is to provide printing ink.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a printing ink composition using a urethane resin obtained by reacting a compound having an amino group or an imino group as a binder solves plate fogging, Completed the invention.

  That is, the present invention relates to an ink resin composition containing a polyurethane resin (a) reacted with a compound (I) having an amino group and / or an imino group covalently bonded to carbon in the resin, and the composition. Provided are a printing ink contained, a printed matter using the printing ink, and a laminate laminate using the printing ink.

  ADVANTAGE OF THE INVENTION According to this invention, printing ink with favorable plate fog property and favorable pigment stability, its printed matter, or a laminated laminate can be provided.

  The urethane resin used in the present invention is not particularly limited as long as a component having an amino group, an imino group and a derivative thereof is bonded to a side chain or a main chain, and various urethane resins can be used.

In order to bind a component having an amino group, an imino group or a derivative thereof to the side chain or main chain of the urethane resin, for example, the following method can be mentioned.
(1) When a urethane resin is produced by reacting polyols and polyisocyanates, a compound (I) having an amino group and / or an imino group covalently bonded to carbon in the resin [hereinafter referred to as compound (I) ). ] To add and react.
(2) A method in which polyols and polyisocyanates are reacted in excess of isocyanate groups, and the resulting isocyanate-terminated urethane resin is reacted with compound (I).
(3) A method in which polyols and polyisocyanates are reacted in excess of isocyanate groups, and the resulting isocyanate-terminated urethane resin is reacted with compound (I) and a chain extender.

  Examples of the polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3-propanediol, 1, 3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol Saturated, such as triethylene glycol, polypropylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol Tired Low molecular polyols; adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelain Polyester polyols obtained by dehydration condensation or polymerization of polyvalent carboxylic acids such as acid, sebacic acid, trimellitic acid, pyromellitic acid or their anhydrides; oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran For example, polyether polyols obtained by polymerization using water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, or other low molecular weight polyols as initiators; the polyether polyols and the carboxylic acids or these And the like, such as ester compounds

  Examples of the polyisocyanate compound include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, and dialkyldiphenylmethane diisocyanate. Aromatic diisocyanates such as tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate; butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2, Aliphatic diisocyanates such as 2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, etc. Diisocyanate; m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride and dimer acid carboxyl group converted to isocyanate group Dimerized isocyanate and the like.

  Examples of the compound (I) having an amino group and / or imino group covalently bonded to carbon in the resin used in the present invention include polyethyleneimine, polyvinylamine, polyallylamine, polyornithine, polylysine and polyamidoamine.

  The polyallylamine polymerizes N, N-dimethylallylamine, N, N-diethylallylamine, N, N-dipropylallylamine, and N, N-dibutylallylamines as monomers forming N, N-dialkylallylamine units. Is obtained. Examples of these include, for example, various products of PAA manufactured by Knitbow Medical Co., Ltd.

  The polyethyleneimine is obtained by polymerizing ethyleneimine. Examples of these include Nippon Catalytic Epomin Co., Ltd. Moreover, the said polyvinylamine is obtained by hydrolyzing the polymer of N-vinyl carboxylic acid amide, for example. Examples of these include, for example, various products of Dianitics Co., Ltd. Examples of the polyamidoamine include an anamide manufactured by Air Products.

  The polyornithine and polylysine can be obtained by polycondensing a carboxyl group and an amino group that ornithine and lysine respectively have in the molecule.

  Since the polyvinylamine or polyamidoamine has an amino group or imino group in the molecule, it reacts easily with the urethane resin in which the isocyanate group remains by using active hydrogens of these functional groups.

  In addition, if the polyurethane resin (a) in this invention has a urethane structure in frame | skeleton, it will not specifically limit, A polyurethane, a polyurethane polyurea, etc. are included.

  In the resin composition for inks of the present invention, as a preferred form of the polyurethane resin (a) that can be dissolved in a single organic solvent, a mixture of a polyester diol (A) and a polyether diol (B), and an isocyanate compound It is a polyurethane polyurea resin obtained by reacting the urethane prepolymer obtained by reacting (C) with the compound (I), the chain extender (D) and the reaction terminator (E).

  The mixing ratio [(A) / (B)] (weight ratio of solid content) of the polyester diol (A) and the polyether diol (B) is 15 or more because the heat resistance of the cured product is good. In view of good substrate adhesion of the cured product, it is preferably 85 or less, and [(A) / (B)] is particularly preferably 30/70 to 70/30.

  In the ratio of the above (A) and (B), the polyester diol (A) preferably has a number average molecular weight of 400 or more because of good coating film adhesion and solubility in an alcohol solvent. Is preferably a number average molecular weight of 3000 or less.

  Further, the polyether diol (B) preferably has a number average molecular weight of 400 to 4,000.

  The ratio (NCO / OH) of the hydroxyl group (OH) in the polyester diol (A) and the polyether diol (B) to the isocyanate group (NCO) in the isocyanate compound (C) is 2.0 to 3.0. It is preferable. When the ratio is less than 2.0, sufficient alkali resistance tends not to be obtained. When the ratio is more than 3.0, the solubility of the resulting prepolymer tends to decrease.

  The polyurethane polyurea resin described above preferably has at least one of a hydroxyl group, a carboxyl group, and a thiol group in the molecule.

  In order to introduce a carboxyl group into the molecule, dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dimethylolalkanoic acid such as dihydroxypropionic acid, dihydroxysuccinic acid And dihydroxybenzoic acid. In particular, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferable from the viewpoint of reactivity and solubility.

The dihydroxycarboxylic acid needs to be blended in the range of 0.5 to 4.0% by weight of the total amount of the dihydroxycarboxylic acid, including the dihydroxycarboxylic acid.
If the total solid content is less than 0.5% by weight, the effect of reducing the trapping failure is poor. If the total solid content exceeds 4.0% by weight, the viscosity of the resin is remarkably increased or gelation is desirable. This is not preferable because the pigment / resin ratio cannot be achieved so as to achieve both the printing viscosity and the physical properties of the ink film.

  In order to introduce a hydroxyl group into the molecule, an alkanolamine having 2 to 20 carbon atoms (mono-, di- or triethanolamine, isopropanolamine, aminoethylethanolamine, etc.) is preferable.

  Examples of the compound having a thiol group include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto. -1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2 -Mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like are preferable.

  The compound (I) used in the present invention is preferably contained in an amount of 0.1 to 2% by weight of the polyurethane resin from the viewpoint of improving plate fogging in addition to drying and adhesion.

  In the preparation process of the polyurethane polyurea resin used in the printing ink of the present invention, the amino group-containing chain extender (D) used for the urethane prepolymer includes ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophorone. In addition to diamine, dicyclohexylmethane-4,4′-diamine, etc., 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, Di-2-hydroxyethylpropylenediamine, (N-aminoethyl) -2-ethanolamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrrole Ethylenediamine, amines having a hydroxyl group in the molecule, such as di-2-hydroxypropyl ethylenediamine can also be used. Furthermore, a reaction terminator (E) can also be used. Examples of such a reaction terminator include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator particularly when it is desired to introduce a carboxyl group into the polyurethane polyurea resin.

  In addition, since the carboxylic acid is introduced into the resin by using dihydroxycarboxylic acid, the ink coating film is hardly dissolved by the ionic bond with the amino group introduced at the resin terminal, which is preferable in terms of improving the trapping failure. .

  The printing ink using the resin composition for ink of the present invention will be described below.

  Examples of the white colorant used in the printing ink of the present invention include organic and inorganic pigments and dyes used in general inks, paints, and recording agents. Specific examples include titanium oxide, zinc oxide, aluminum oxide, calcium carbonate, zinc sulfide, magnesium oxide, barium sulfate, magnesium sulfate, chromium oxide, and silica. In particular, it is preferable to use titanium oxide from the viewpoints of colorability, hiding properties, chemical resistance, weather resistance, and the like.

  Examples of inorganic pigments other than white pigments include pigments such as carbon black, aluminum, mica (mica), and bengara (iron (III) oxide). Aluminum is generally in the form of a powder or paste, but is preferably used in the form of a paste from the viewpoint of easy handling and safety for the human body, and a leafing or non-leafing type is used depending on the demand for brightness and density.

  Examples of the colored colorant used in the printing ink of the present invention include organic and inorganic pigments and dyes used in general inks, paints, and recording agents. For example, pigments such as azo, phthalocyanine, dioxazine, quinacridone, anthraquinone, perinone, perylene, thioindigo, isoindolinone, quinophthalone, azomethine azo, diketopyrrolopyrrole, isoindoline, etc. Can be mentioned.

  The colorant is preferably contained in a proportion of 1 to 50% by mass with respect to the total weight of the printing ink in order to develop a sufficient concentration and coloring power in the printing ink. These colorants can be used alone or in combination of two or more.

  When the pigment is stably dispersed in the printing ink of the present invention, the resin alone can be dispersed, but a dispersant can be used in combination for further dispersing the pigment stably. For example, cationic, anionic, nonionic, amphoteric surfactants can be used. The amount of the dispersant used is preferably 0.05% by mass or more with respect to the total weight of the ink from the viewpoint of the storage stability of the ink and 5% by mass or less from the viewpoint of the suitability for lamination. Furthermore, it is especially preferable that it is contained in the range of 0.1 to 2 mass%.

  The printing ink of the present invention can be produced by dissolving or dispersing a resin, a colorant and the like in a solvent. Specifically, a pigment dispersion in which a pigment is dispersed in an organic solvent with the resin, and if necessary, with the dispersant is manufactured, and other compounds are blended with the obtained pigment dispersion as necessary. Thus, an ink can be produced.

  The particle size distribution of the pigment dispersion can be optimized by appropriately adjusting the diameter of the grinding media of the dispersion grinder, the filling rate, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. it can. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

  The viscosity of the printing ink produced by the above method is 10 mPa · s or more at a liquid temperature of B-type viscometer at 25 ° C., from the viewpoint of preventing the precipitation of the pigment and dispersing it appropriately. From the viewpoint, it is preferably in the range of 1000 mPa · s or less.

  The printing ink of the present invention can be used in known printing methods such as gravure printing and flexographic printing. For example, it is diluted with a diluent solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed.

  The printing ink of the present invention can be obtained as a printed matter and a covering by applying the printing and application to the various film and sheet-like substrates using the above printing method, and drying and fixing by oven drying. . Film and sheet base materials include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide and poly Examples include vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, and composite materials thereof.

  The base material may be subjected to vapor deposition coating treatment and / or polyvinyl alcohol coating treatment on the surface of metal oxide or the like, and may further be subjected to surface treatment such as corona treatment.

  Furthermore, the usual extrusion lamination (extrusion laminating) method in which molten polyethylene resin is laminated on the printed surface of the printed material through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printed surface The printing ink of the present invention was used by a known laminating process such as a dry laminating method in which an adhesive such as a system is applied and a plastic film is laminated, or a direct laminating method in which a molten polypropylene is directly pressed and laminated on a printing surface. Laminate laminate is obtained

  The printing ink of the present invention can easily recover and reuse the solvent vapor generated in the printing and drying processes. More preferably, a single alcohol solvent and a polyurethane polyurea resin soluble in the alcohol are used, and the alcohol component can be easily separated and recovered from the solvent vapor generated in the printing and drying processes. The recovered solvent is a single alcohol, and unlike the ester solvent, there is no by-product such as carboxylic acid, and the purification process can be simplified.

  Hereinafter, the present invention will be specifically described with reference to examples. In the examples, “part” and “%” are based on weight unless otherwise specified.

(Production Example 1: Preparation of polyurethane polyurea resin)
A 0.5-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction pipe was charged with a hydroxyl value of 112.2 (mgKOH / g) and a molecular weight of 1,000. -Condensate of methyl-1,5-pentanediol and adipic acid 15.9 parts, hydroxyl value 112.2 (mg KOH / g), molecular weight 1,000 polypropylene glycol 143.1 parts, hydroxyl value 56.1 ( mg KOH / g), 19.0 parts of polyethylene glycol monomethyl ether having a molecular weight of 1,000, 0.9 part of 1,1,1-trimethylolpropane, and 1.6 parts of 2-2bis (hydroxymethyl) propionic acid, Nitrogen gas was allowed to flow and the temperature was raised to 50 ° C. with stirring. Subsequently, 84.3 parts of isophorone diisocyanate was added and reacted at 90 ° C. until NCO%, which is the residual ratio of isocyanate groups, reached 6.0% to obtain a urethane prepolymer (A1). Subsequently, in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube, 694.0 parts of 2-propanol, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane 28.6 parts, di-n-butylamine 5.0 parts, polyallylamine PAA-03 (manufactured by Nittobo Medical Co., Ltd.) 7.6 parts, and the temperature was raised to 40 ° C. Next, 264.8 parts of urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to give a polyurethane having a solid content of 30%, a weight average molecular weight of 11,200, and an amine value of 1.2 (mgKOH / g). An alcohol solution (X1) of polyurea resin was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Production Example 2: Preparation of polyurethane polyurea resin)
A 0.5 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction pipe was charged with a hydroxyl value of 56.1 (mgKOH / g) and a molecular weight of ε. -Polycaprolactone diol 36.2 parts mainly composed of caprolactone, hydroxyl value 37.4 (mgKOH / g), polypropylene glycol 108.6 parts with a molecular weight of 3,000, hydroxyl value 56.1 (mgKOH / g), molecular weight 36.2 parts of polytetramethylene glycol of 2,000, hydroxyl value 102.0 (mgKOH / g), 44.2 parts of polyethylene glycol monomethyl ether of molecule 550, 3.6 parts of 1,1,1-trimethylolpropane The mixture was charged, nitrogen gas was flowed, and the temperature was raised to 50 ° C. with stirring. Subsequently, 32.8 parts of isophorone diisocyanate was added and reacted at 90 ° C. until NCO%, which is the residual ratio of isocyanate groups, reached 5.8%, to obtain a urethane prepolymer (A2).
Subsequently, in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube, 687.4 parts of 2-propanol, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane 28.1 parts, di-n-butylamine 7.2 parts, 15.7 parts of a 20% aqueous solution of polyallylamine (paa-6) obtained in Production Example 6 described later, The temperature was raised to ° C. Next, 261.6 parts of urethane prepolymer (A2) was added and reacted at 40 ° C. for 4 hours to give a polyurethane having a solid content of 30%, a weight average molecular weight of 13,800, and an amine value of 0.7 (mgKOH / g). An alcohol solution (X2) of polyurea resin was obtained. Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Production Example 3: Preparation of polyurethane polyurea resin)
In a 2-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube, 682.3 parts of 2-propanol, 1-amino-3-aminomethyl-3, 5, 20.9 parts of 5-trimethylcyclohexane, 10.2 parts of di-n-butylamine and 22.1 parts of polyallylamine PAA-03 (manufactured by Nittobo Medical Co., Ltd.) were added, and the temperature was raised to 40 ° C. Next, 264.4 parts of urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to give a polyurethane having a solid content of 30%, a weight average molecular weight of 14,500, and an amine value of 1.2 (mgKOH / g). An alcohol solution (X3) of polyurea resin was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Production Example 4: Preparation of polyurethane polyurea resin)
In a 2-liter four-necked flask equipped with a stirrer, thermometer, Dimroth reflux condenser, and nitrogen gas inlet tube, 700.0 parts of 2-propanol, 1-amino-3-aminomethyl-3, 5, 21.8 parts of 5-trimethylcyclohexane, 12.1 parts of di-n-butylamine, Epomin SP-018 (Nippon Shokubai Polyethyleneimine, molecular weight of about 1800)] were added and the temperature was raised to 40 ° C. Next, 263.9 parts of urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to give a polyurethane having a solid content of 30%, a weight average molecular weight of 12,200, and an amine value of 1.2 (mgKOH / g). An alcohol solution (X4) of polyurea resin was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Production Example 5: Preparation of polyurethane polyurea resin)
In a 2-liter four-necked flask equipped with a stirrer, thermometer, Dimroth reflux condenser, and nitrogen gas inlet tube, 700.0 parts of 2-propanol, 1-amino-3-aminomethyl-3, 5, 28.0 parts of 5-trimethylcyclohexane, 5.0 parts of di-n-butylamine and 3.1 parts of ancamide 375A (polyamideamine manufactured by Air Products) were added, and the temperature was raised to 40 ° C. Next, 263.9 parts of urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to give a polyurethane having a solid content of 30%, a weight average molecular weight of 11,500, and an amine value of 1.2 (mgKOH / g). An alcohol solution (X5) of polyurea resin was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

Production Example 6
To 1100 g of concentrated hydrochloric acid (65%), 570 g (10 mol) of monoallylamine is added dropwise with stirring at 5 to 10 ° C. under water cooling. After completion of the dropwise addition, water and excess hydrogen chloride were distilled off at 60 ° C. under reduced pressure to obtain white crystals. The obtained crystals are dried at 80 ° C. under reduced pressure. In a 2 liter round bottom flask equipped with a stirrer, thermometer, back-flow condenser, and nitrogen gas inlet tube, 590 g of the dried crystals were dissolved in 210 g of water to prepare a 70% aqueous solution of monoallylamine hydrochloride. The solution is warmed to 50 ° C. while passing nitrogen gas. Azo initiator: 14 g of 2,2′-bis (N-phenylamidinyl) -2,2′-azopropane dihydrochloride is dissolved in 20 ml of distilled water and added. Since it generates heat after 2 hours, it is cooled while stirring and kept at a liquid temperature of 48 to 52 ° C. Ten hours after the addition of the initiator, stirring was stopped, and the resulting solution was added to excess methanol to obtain a white polymer (polyallylamine hydrochloride) precipitate. The resulting precipitate is filtered off and washed with methanol to remove monoallylamine hydrochloride.
Next, 30 g of the obtained polyallylamine hydrochloride was dissolved in 270 g of distilled water, hydrochloric acid was removed through a strongly basic ion exchange resin (Amberlite-IRA-402), and the developing solution (polyallylamine aqueous solution) was freeze-dried. Polyallylamine (paa-6) was obtained.
The resulting polyarylamine had a weight average molecular weight of 2000.

(Comparative Production Example 1: Preparation of polyurethane polyurea resin)
In a 2-liter four-necked flask equipped with a stirrer, thermometer, Dimroth reflux condenser, and nitrogen gas inlet tube, 700.0 parts of 2-propanol, 1-amino-3-aminomethyl-3, 5, 32.6 parts of 5-trimethylcyclohexane and 7.2 parts of di-n-butylamine were added, and the temperature was raised to 40 ° C. Next, 260.2 parts of urethane prepolymer (A2) was added and reacted at 40 ° C. for 4 hours to give a polyurethane having a solid content of 30%, a weight average molecular weight of 18,500, and an amine value of 0.7 (mgKOH / g). An alcohol solution (Y1) of polyurea resin was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

Examples 1 to 5 and Comparative Example 1 will be specifically described.
(Black ink preparation method)

Example 1
If 100 parts of 1.5 mm glass beads are charged in a glass bottle and Example 1 is taken as an example, 44 parts of IPA and 11 parts of MONARCH 460 (manufactured by Cabot Specialty Chemicals, Inc.) as carbon black are obtained in Production Example 1. After adding 40 parts of polyurethane polyurea resin X1 and 5 parts of water, dispersion was performed with a paint conditioner for 1 hour, and then the glass beads were filtered with a wire mesh to obtain black ink XB-1.

Examples 2-5
Using the resins obtained in Production Examples 2 to 5, inks were prepared in the same procedure as in Example 1 at the blending ratios shown in Table 1.

Comparative Example 1
Using resin Y1 obtained in Comparative Production Example 1, an ink was prepared in the same procedure as in Example 1 at the blending ratio shown in Table 2.

Comparative Example 2
100 parts of 1.5mm glass beads in a glass bottle, 43 parts of IPA, 11 parts of MONARCH 460 (Cabot Specialty Chemicals, Inc.) as carbon black, 1 part of Floren G-700 (manufactured by Kyoeisha Chemical Co., Ltd.) After adding 40 parts of polyurethane polyurea resin Y1 and 5 parts of water, dispersion was performed with a paint conditioner for 1 hour, and then the glass beads were filtered with a wire mesh to obtain black ink YB-2.

  The following evaluation was implemented about the ink of Examples 1-5 obtained above and the ink of Comparative Examples 1-2.

(Liquidity)
The viscosities of the inks listed in Tables 1 and 2 were measured with a B-type viscometer at 6 rpm and 60 rpm. The viscosity measured at 6 rpm was divided by the viscosity measured at 60 rpm to determine the TI value. If the TI value is less than 3.0, it can be used practically.
(Evaluation)
◯: TI value is less than 1.5 Δ: TI value is 1.5 or more and less than 3.0 ×: TI value is 3.0 or more

(Adhesion)
The inks listed in Tables 1 and 2 are developed on a treated surface of a biaxially stretched polyethylene terephthalate film (E5102, 12 μm, manufactured by Toyobo Co., Ltd.) having a corona discharge treatment on one side by a bar coater # 4. After the Nichiban cellophane tape 18 mm width was brought into close contact with the color development surface, the cellophane tape was peeled off vigorously in the vertical direction, and the area ratio of the ink film adhering to the cellophane tape was visually evaluated.
If the area ratio of the ink adhering to the cellophane tape is less than 30%, it can be judged as a practical level.
(Evaluation)
A: Area ratio of ink adhering to cellophane tape 0%
○: Area ratio of ink adhering to cellophane tape is less than 10% Δ: Area ratio of ink adhering to cellophane tape is less than 30% ×: Area ratio of ink adhering to cellophane tape is 30% or more XX: Adhering to cellophane tape More than 80% ink area ratio

(Plate cover)
The inks listed in Tables 1 and 2 were diluted with IPA, and diluted with Zaan Cup No. 3 manufactured by Koiso Co., Ltd. so as to be 16 seconds. The adjusted ink is printed on the treated surface of a biaxially stretched polypropylene film (Pyrene P-2161 20 μm, manufactured by Toyobo Co., Ltd.) subjected to corona discharge treatment on one side using a gravure printing machine equipped with a semi-solid plate. It was. The printing speed is changed to 100 m / min, 150 m / min, and 200 m / min. The ink in the non-image area of the semi-solid plate is not scraped off, and the leaked ink is transferred to the biaxially stretched polypropylene film (plate The degree of occurrence of fogging was visually evaluated. If the plate fog phenomenon does not occur under the printing conditions of 100 m / min, it can be determined that the level is practical. However, it is desirable that the plate fog phenomenon does not occur even at a higher printing speed.
(Evaluation)
◎: No plate fog phenomenon occurs at a printing speed of 200 m / min. ○: No plate fog phenomenon occurs at a printing speed of 150 m / min. Δ: No plate fog phenomenon occurs at a printing speed of 100 m / min. X: Printing speed of 100 m Plate fog phenomenon occurs at / min. XX: Plate fog phenomenon occurs severely at a printing speed of 100m / min.

(Metastatic)
The inks listed in Tables 1 and 2 were diluted with IPA, and diluted with Zaan Cup No. 3 manufactured by Koiso Co., Ltd. so as to be 16 seconds. It printed on the processing surface of the biaxially-stretched polypropylene film (Toyobo Co., Ltd. pyrene P-2161 20micrometer) which gave the corona discharge process to one side using the gravure printing machine which attached the gradation plate. The printing speed was changed to 50 m / min and 80 m / min, and the presence or absence of missing ink (scratch) in the highlight portion (cell volume: 5%, 10%) of the gradation plate was visually evaluated. Although it can be determined that it is a practical level if no blurring occurs in the 10% cell volume under printing conditions of a printing speed of 80 m / min or more, it is desirable that no blurring occurs even at a lower printing speed and at a lower cell volume%.
(Evaluation)
◎: No blurring at a printing speed of 50 m / min. ○: No blurring at a printing speed of 80 m / min. Δ: Scratching occurs at a printing speed of 80 m / min and a cell volume of 5%, but a cell volume of 10%.
No blurring occurred: Scratch can be remarkably confirmed even at a printing speed of 80 m / min and a cell volume of 10%.

The raw materials in the table are as follows.
MONARCH 460 (manufactured by Cabot Specialty Chemicals, Inc.): carbon black, particle size 27 nm, BET specific surface area 84 m ² / g
Florene G-700 (manufactured by Kyoeisha Chemical Co., Ltd.): modified carboxy group-containing polymer

(Measurement of number average molecular weight, weight average molecular weight)
The number average molecular weight and the weight average molecular weight were measured by the following methods.
・ GPC (polystyrene conversion)
-Tosoh Co., Ltd. HLC8220 system-Conditions Separation column: Four TSKgelGMHHR-N made by Tosoh Co., Ltd. are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.

Claims (9)

  A resin composition for ink containing a polyurethane resin (a) reacted with a compound (I) having an amino group and / or an imino group covalently bonded to carbon in the resin.   The compound (I) having the amino group and / or imino group is at least one compound selected from the group consisting of polyethyleneimine, polyvinylamine, polyallylamine, polyornithine, polylysine and polyamidoamine. Resin composition for ink. The polyurethane resin (a) is a urethane prepolymer obtained by reacting one or more diols selected from the group consisting of polyester diols, polyether diols, dihydroxy carboxylic acids, and alkyl diols with isocyanate compounds, the amino groups and 2. The resin composition for ink according to claim 1, which is a resin obtained by reacting the compound (I) having an imino group, an amino group-containing chain extender, and a reaction terminator.   The resin composition for ink as described in any one of Claims 1-3 containing a pigment.   Furthermore, the resin composition for inks as described in any one of 1-4 containing an organic solvent. 6. The resin composition for ink according to claim 5, wherein the organic solvent is a single solvent component (b) selected from the group consisting of alcohol, ketone and acetate.   Printing ink using the resin composition for ink as described in any one of Claims 1-6.   A printed matter using the printing ink according to claim 7.   A laminate laminate using the printing ink according to claim 7.